CN109125773B

CN109125773B - Plasma sterilization indicator

Info

Publication number: CN109125773B
Application number: CN201811005190.0A
Authority: CN
Inventors: 汤百灿
Original assignee: Guangzhou Mofu Material Technology Co ltd
Current assignee: GUANGZHOU BAOLI BANGDE HIGH POLYMER MATERIAL CO LTD
Priority date: 2018-08-30
Filing date: 2018-08-30
Publication date: 2020-09-15
Anticipated expiration: 2038-08-30
Also published as: CN109125773A

Abstract

The patent relates to the field of plasma sterilization indication, and discloses a plasma sterilization indicator, which at least comprises more than one dye capable of generating color conversion under the action of hydrogen peroxide plasma, and a pyridine derivative capable of fixing color in an indicator system. The plasma sterilization indicator has obvious color change before and after hydrogen peroxide plasma sterilization, the color after sterilization does not return to the original color, the color stability is excellent, and whether a sterilization target object is subjected to a sterilization process or not can be reliably judged; the introduction of the pyridine derivative can control the color change speed of the dye in hydrogen peroxide plasma, so that whether the sterilization condition of the sterilization target object is proper or not can be judged through the change of the color tone.

Description

Plasma sterilization indicator

Technical Field

The present invention relates to the field of plasma sterilization indication, and more particularly, to a plasma sterilization indicator that, when hydrogen peroxide low-temperature plasma is used to sterilize a sterilization target, confirms whether the sterilization target has been subjected to a sterilization process or whether sterilization has been effectively performed, by changing the color tone of the sterilization target.

Background

With the rapid development of medical health and health care and the continuous improvement of medical technology, various precision instruments and equipment are gradually popularized and applied, and the equipment can not be sterilized at high temperature (mainly high-temperature high-pressure steam and high-temperature dry heat). In order to solve this problem, various low-temperature chemical sterilization methods have been developed, such as ethylene oxide low-temperature sterilization applied to hospital sterilization in the 50 th century, and ethylene oxide sterilizers are widely used by some large-city hospitals in the U.S. and china by the middle of the 90 th century. The epoxy ethane has the function of killing various microorganisms such as bacteria, spores, fungi, viruses and the like; the sterilization mechanism is combined with amino, hydroxyl, carboxyl or sulfydryl in bacterial protein molecules, enzymes and nucleic acid to damage the bacterial cells, thereby achieving the sterilization effect. However, ethylene oxide is toxic and is a suspected carcinogen, and besides extremely strict indoor air concentration control, complicated purification and emission treatment is also needed, so that the operation period is long; the other widely used method is low-temperature steam formaldehyde sterilization, the sterilization mechanism of the method is similar to that of ethylene oxide, and the method also has the defects of gas toxicity, strict concentration control and purification treatment, long sterilization operation period and the like.

In the 90 s of the 20 th century, plasma sterilization began to be a pilot test as a new low temperature sterilization technique. Plasma is generated by gas under the action of heating or strong electromagnetic field, and mainly comprises electrons, ions, atoms, molecules, active free radicals, rays and the like, namely the gas slurry is called as a material aggregation state. The existing plasma sterilization is mainly performed by exciting hydrogen peroxide (H2O2) into 'gas slurry' for sterilization, wherein the hydrogen peroxide (H2O2) is an active oxidant, and the decomposition products of the hydrogen peroxide are water and nascent oxygen. The sterilization mechanism of hydrogen peroxide plasma is mainly caused by the combined action of ultraviolet rays, high-energy particles and active free radicals, wherein active substances such as active free radicals, hydrogen peroxide radicals and hydroxyl radicals are combined with proteins and nucleic acids in bacteria to destroy the metabolism of the bacteria, so that the sterilization effect is achieved. The hydrogen peroxide low-temperature plasma sterilization system has the characteristics that: the sterilization speed is high, only about 55 minutes is needed, and the detoxification time is not needed; no toxic substance is left, and the final decomposition product is water and oxygen which are safe for the environment and medical staff. Therefore, the hydrogen peroxide low-temperature plasma sterilization system (particularly GB/T32309-2015) can be used for sterilizing medical instruments and also used in the industries and works requiring sterilization of sanitary materials, food, tableware and the like.

Important in the application of these sterilization methods are: whether the equipment to be sterilized is subjected to the sterilization process is judged, and whether the sterilization effect on the equipment is proper is checked. On the other hand, indicator compositions that change color tone during sterilization have become a means of determining whether sterilization has been performed or a means of inspecting whether the sterilization effect is appropriate.

Various indicator compositions exist for indicating the presence of hydrogen peroxide based on the principle of acid-base titration. Acid-base indicators each having a different pKa value and thus a different acid-base indicating color, such as: methyl violet, picric acid, methyl green, malachite green, cresol red, methyl violet, thymol blue, methyl violet, alizarin yellow R, dimethyl yellow, bromophenol blue, congo red, alizarin red, bromocresol green, methyl red, bromophenol red, bromocresol purple, bromothymol blue, neutral red, phenol red, cresol red, phenolphthalein, thymolphthalein, alizarin red S, alizarin yellow R, dandan yellow, and the like. The applicable acid-base indicator is matched with iodide, metal salt, transition metal salt and the like, and the applicable aqueous polymer solution is matched with hydrogen sulfide, sodium hypochlorite and the like to be soaked in the filter test paper; the hydrogen peroxide forms plasma under the action of high-frequency electromagnetic field in the sterilizer, and active factors such as free radical HO, perhydroxyl free radical HO2, excited H2O2, active oxygen atom O, active hydrogen atom H and the like in the plasma react with the active factors to generate color change, so that the prepared test paper can detect the hydrogen peroxide. Also, some products in the form of printing ink are applied to a hydrogen peroxide low-temperature plasma sterilization system based on the chemical action, but the finished indicator product is unstable before and after use, such as the product is influenced by external air moisture and acid and alkali substances of contact products, the indicator changes are not obvious after being stored for a long time, or the indicator fades during the recording period after being processed by the sterilization system, and the like, which all affect the daily management of a hospital supply center.

Disclosure of Invention

In view of the above, the present disclosure provides a stable and effective plasma sterilization indicator for a hydrogen peroxide low-temperature plasma sterilization system to overcome at least one of the disadvantages of the prior art. The patent is based on a hydrogen peroxide low-temperature plasma sterilization system and aims to prepare an indicator in the form of printing ink, wherein the appearance color of the ink indicator is obviously changed by exposure to hydrogen peroxide plasma; whether the articles and the instruments are sterilized by the hydrogen peroxide plasma or not can be effectively judged through the intuitive color change, or whether the hydrogen peroxide plasma is completely and effectively diffused in the system or not can be judged.

In order to solve the technical problems, the patent adopts the following technical scheme:

a plasma sterilization indicator comprises at least more than one dye capable of generating color transformation under the action of hydrogen peroxide plasma, and a pyridine derivative for fixing color in an indicator system.

The hydrogen peroxide plasma sterilization indicator is substantially the same as the dye used in the ethylene oxide gas sterilization indicator. However, because the sterilization mechanisms of the ethylene oxide gas and the dye are different, the ethylene oxide gas kills the thalli through alkylation, and the hydrogen peroxide plasma kills the thalli through stronger (radio frequency ion) oxidation, so the dye discoloration mechanisms of the ethylene oxide gas and the dye are different, and the ethylene oxide gas and the dye can be stably generated or degenerated into another color after the reaction; however, even if hydrogen peroxide having a strong oxidizing action reacts with a dye after the hydrogen peroxide plasma is generated in the sterilizer, the indicator may not change color, or may change color but may be unstable or may not change color after being left for a long time. Therefore, the present invention introduces a pyridine derivative into the indicator as a discoloration inhibitor for a discolored dye generated in a hydrogen peroxide plasma sterilization treatment, thereby more stably generating discoloration.

Further, the pyridine derivative is one or more of pyridone, pyrithione or a pyrithione salt.

The pyridine derivative and the dye generate other colors under the fading or matching action under the action of hydrogen peroxide with strong oxidation effect, and the action of the pyridine derivative is very critical and important, influences and controls the color development speed and the color development stability, and plays a role in controlling the color development speed and the color fixation stably.

Further, the pyrithione salt is one or more of copper pyrithione, zinc pyrithione, sodium pyrithione, magnesium pyrithione, cadmium pyrithione, zirconium pyrithione, and the like.

The vat dyes and sulfur vat dyes can obviously change color under the action of [ O ], [ H ] ion free radicals, and based on the dyes described in the patent, at least one of the vat dyes and sulfur vat dyes is preferably selected, the dyes can be reduced into soluble leuco body sodium salts in alkaline solution, most of the leuco body sodium salts have lighter color or colorless color (the parts are just opposite), and the leuco body sodium salts can change the original color under the oxidation action of air or other oxidants. If some indigo vat dye leuco bodies are colorless, but are dark blue after being oxidized and reduced; for example, the leuco body of the anthraquinone vat dye is light yellow after being oxidized and reduced to red. Although other dyes have color conversion, the color difference is not higher than that of vat dyes and sulfur vat dyes; obvious front and back color difference can well play a role in indicating.

The pyridine derivative is preferably a pyridine derivative having an ionizing group. The vat dye and the sulfur vat dye are not dissolved in an aqueous system, although the leuco dye can be dissolved in the aqueous system, a non-aqueous solution can be generated along with the reduction of the pH value of the system, and the introduced copper pyrithione, sodium pyrithione and zinc pyrithione with ionized groups can stabilize the system and play a role in improving the plasma sensitivity.

The vat dye comprises at least one of anthraquinone vat dyes and indigoid vat dyes.

The anthraquinone vat dye is a vat dye synthesized by anthraquinone or derivatives thereof and a dye with an anthraquinone structure. Most of the leuco acid sodium salts of the dyes are darker than unreduced color, and only a few leuco acid sodium salts are similar to unreduced color, which is caused by that the anthraquinone without conjugated double bonds generates coherent conjugated double bonds after being reduced into the leuco acid sodium salts. The chemical reaction principle is as follows:

the chemical reaction principle of the indigoid vat dye is as follows:

the vat dye comprises at least one of vat yellow WG, vat orange 6RTK, vat yellow FFRK, vat blue RS, RSN, vat blue BC, vat blue GCDN, vat blue 3G, 5G, vat green BB, vat yellow G, vat gold orange, vat deep blue OB, vat deep blue RB, vat black BB, vat green B, FFB, red purple R, bright purple 3B, bright purple RR, purple red RRK, vat yellow GC, brilliant green FFB, indigo No. 1, vat blue 2B, vat red 5B, pink R, vat brown RRD, red purple RH, RRN, pink FFB, scarlet B, vat purple BBF, vat scarlet R, vat black B, golden yellow GK, vat bright orange GK, bright blue 4G.

The sulfur vat dyes include sulfur yellow 2G, sulfur brilliant blue CLB, sulfur blue RN, BN, BRN, sulfur new blue BBF, sulfur dark blue 3R, RL, sulfur red brown 3B, sulfur black BN, sulfur vat blue R, sulfur vat black CLN, sulfur yellow brown, sulfur red brown, etc.

The plasma sterilization indicator of the present invention further comprises at least one suitable aqueous polymeric resin vehicle.

The waterborne polymer resin binder selected and applied by the invention comprises cellulose derivatives, waterborne polybutadiene resin, waterborne epoxy resin, waterborne alkyd resin, waterborne polyester resin, waterborne polyurethane resin, waterborne acrylate emulsion and the like. The cellulose derivative comprises at least one of hydroxymethyl cellulose (CMC), Methylcellulose (MC), hydroxyethyl cellulose (HEC), hydroxyethyl methylcellulose (HEMC), hydroxypropyl cellulose (HPC), and hydroxypropyl methylcellulose (HPMC).

In the invention, one or two different types of waterborne polyurethane emulsion and another or two different types of waterborne acrylate emulsion are preferably compounded for application.

The plasma sterilization indicator also comprises one or more of defoaming agent, flow aid, filler, pigment, plasticizer, surfactant, wetting dispersant, thickener, film forming aid and surfactant. The filler comprises one or more of titanium dioxide, lithopone and zinc oxide.

The indicator is suitable for printing materials of various non-hygroscopic materials, such as synthetic paper materials of PVC, PP, PET and the like.

This patent compares with prior art has following beneficial effect:

the plasma sterilization indicator has obvious color change before and after hydrogen peroxide plasma sterilization, the color after sterilization does not return to the original color, the color stability is excellent, and whether a sterilization target object is subjected to a sterilization process or not can be reliably judged; the introduction of the pyridine derivative can control the color change speed of the dye in hydrogen peroxide plasma, so that whether the sterilization condition of the sterilization target object is proper or not can be judged through the change of the color tone.

Detailed Description

This patent is described in further detail below with reference to specific examples.

Example 1

In this embodiment, the plasma sterilization indicator includes the following components in parts by weight:

dye: 5 parts of reactive red B and 0.5 part of OB dye blue;

pyridine derivatives: 2 parts of sodium pyrithione;

aqueous polymer resin binder: 30 parts of polyurethane emulsion and 30 parts of acrylic emulsion;

auxiliary agent: 2 parts of nano titanium dioxide, 0.5 part of rheological agent, 0.7 part of film forming agent, 0.1 part of defoaming agent and 10 parts of thickening agent; solvent: deionized water/alcohol 19.2 parts.

Example 2

dye: active blue BF4R 2.4.4 parts, disperse pink R3L 2.0.0 parts;

pyridine derivatives: 2 parts of sodium pyrithione;

aqueous polymer resin binder: 40 parts of polyurethane emulsion and 20 parts of acrylic emulsion;

auxiliary agent: 3 parts of nano titanium dioxide, 0.3 part of rheological agent, 0.7 part of film forming agent, 0.4 part of defoaming agent and 10 parts of thickening agent; solvent: deionized water/alcohol 19.2 parts.

Example 3

dye: 1.0 part of active violet 5R and 0.5 part of vat yellow G;

pyridine derivatives: 1 part of zinc pyrithione and 1 part of barium pyrithione;

aqueous polymer resin binder: 35 parts of polyurethane emulsion and 35 parts of acrylic emulsion

Auxiliary agent: 3 parts of nano titanium dioxide, 0.2 part of rheological agent, 1.0 part of film forming agent, 0.3 part of defoaming agent and 10 parts of thickening agent; solvent: deionized water/alcohol 12.5 parts.

Example 4

dye: 0.4 part of vat black B, 1.0 part of active violet 5R, 0.1 part of disperse blue RRL and 0.2 part of vat yellow G;

pyridine derivatives: 1 part of sodium pyrithione and 1 part of copper pyrithione;

aqueous polymer resin binder: 40 parts of polyurethane emulsion and 30 parts of acrylic emulsion;

auxiliary agent: 5.0 parts of nano titanium dioxide, 0.2 part of rheological agent, 0.8 part of film forming agent, 0.2 part of defoaming agent and 10 parts of thickening agent;

solvent: 10.1 parts of deionized water/alcohol.

Example 5

dye: 3.5 parts of vat blue RS;

pyridine derivatives: 2 parts of sodium pyrithione;

auxiliary agent: 4.0 parts of nano titanium dioxide, 0.5 part of rheological agent, 0.7 part of film forming agent, 0.1 part of defoaming agent and 10 parts of thickening agent;

solvent: deionized water/alcohol 19.2 parts.

Example 6

dye: 4.4 parts of vat yellow WG;

pyridine derivatives: 2 parts of sodium pyrithione;

auxiliary agent: 3 parts of nano titanium dioxide, 0.3 part of rheological agent, 0.7 part of film forming agent, 0.4 part of defoaming agent and 10 parts of thickening agent;

solvent: deionized water/alcohol 19.2 parts.

Example 7

dye: 2.0 parts of reduced indigo and 0.5 part of disperse pink;

pyridine derivatives: 1.5 parts of sodium pyrithione;

aqueous polymer resin binder: 35 parts of polyurethane emulsion and 35 parts of acrylic emulsion;

auxiliary agent: 2 parts of nano titanium dioxide, 0.2 part of rheological agent, 1.0 part of film forming agent, 0.3 part of defoaming agent and 10 parts of thickening agent;

solvent: deionized water/alcohol 12.5 parts.

Example 8

dye: 3.5 parts of reducing orange RF;

pyridine derivatives: 1.5 parts of sodium pyrithione and 0.5 part of cadmium pyrithione;

auxiliary agent: 4 parts of nano titanium dioxide, 0.5 part of rheological agent, 0.7 part of film forming agent, 0.1 part of defoaming agent and 10 parts of thickening agent;

solvent: deionized water/alcohol 19.2 parts.

Example 9

This example differs from example 5 in that the aqueous polymer resin binder comprises 60 parts of aqueous polybutadiene resin, otherwise the example 5.

Example 10

This example is different from example 6 in that the waterborne polymer resin binder comprises 60 parts of waterborne epoxy resin, and the rest is the same as example 6.

Comparative example 1

This comparative example is different from example 1 in that the pyridine derivative is not included in the plasma sterilization indicator, and the other example is the same as example 1.

Comparative example 2

This comparative example is different from example 6 in that the pyridine derivative is not included in the plasma sterilization indicator, and the other example is the same as example 6.

The test method comprises the following steps:

1. the plasma sterilization indicators of the above-described examples and comparative examples were manually coated on a substrate of polypropylene-based synthetic paper (Yupo FGS-250, manufactured by Yupo corporation) using a loop-rod type wet film coater of 0.45m/m to prepare corresponding indicator paper, and the initial color of each indicator paper was recorded in Table 1.

2. The sterilization treatment (2-minute elimination treatment and short-cycle treatment) was performed with a plasma sterilizer (LK/DZK series) of the genu laken medical science and technology ltd, and the discoloration results were recorded in table 1. The 2-minute abatement treatment is a treatment in which the sterilization chamber is depressurized to about 0.5torr, high-frequency energy is applied to the sterilization chamber in this state to produce an air plasma state, the pressure is restored to a first pressure, the sterilization chamber is depressurized to about 0.4torr again, and hydrogen peroxide is injected and diffused for 2 minutes; the short cycle treatment is a treatment in which hydrogen peroxide is diffused for 6 minutes, then slightly decompressed, and then high-frequency energy is applied to produce a low-temperature plasma state of hydrogen peroxide, and then hydrogen peroxide is injected and diffused for 8 minutes to apply high-frequency energy, followed by "2-minute elimination treatment".

3. The color change was recorded in table 1 after placing each indicator paper subjected to hydrogen peroxide plasma sterilization treatment in a constant temperature and humidity chamber at 23 ℃ and 90% RH for 1 month.

TABLE 1 test results

As can be seen from the test results in table 1, the above examples exhibited significant color transition before and after the plasma sterilization treatment, and the color after the transition could be stably present. From the test results of example 1 and comparative example 1, and example 6 and comparative example 2, it can be seen that the pyridine derivative plays a key role in plasma sterilization indication, in example 1, the pyridine derivative is a key factor for indicating whether the indicator undergoes color transition before and after plasma sterilization treatment, and in example 6, the pyridine derivative affects the color difference of the indicator undergoing color transition before and after plasma sterilization treatment; from the test results of example 5 and example 9, and example 6 and example 10, it can be seen that the formulation of the polyurethane emulsion and the acrylate emulsion has obvious advantages compared with other waterborne polymers, better adhesion to various non-hygroscopic substrates, better compatibility with coloring dyes/vat dyes, and no dark color after sterilization treatment.

It should be understood that the above examples of the present patent are only examples for clearly illustrating the present patent, and are not intended to limit the embodiments of the present patent. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of this patent shall be included in the protection scope of the claims of this patent.

Claims

1. A plasma sterilization indicator comprising at least one dye capable of undergoing a color change in response to a hydrogen peroxide plasma, and a pyridine derivative that fixes color in the indicator system, wherein the pyridine derivative is a pyrithione salt.

2. A plasma sterilization indicator according to claim 1, wherein the pyrithione salt is one or more of copper pyrithione, zinc pyrithione, sodium pyrithione, magnesium pyrithione, cadmium pyrithione, zirconium pyrithione.

3. The plasma sterilization indicator of claim 1, wherein the dye comprises at least one of a vat dye, a sulfur vat dye.

4. A plasma sterilisation indicator according to claim 3, wherein the pyridine derivative is a pyridine derivative having an ionized group.

5. A plasma sterilization indicator according to claim 1, wherein the indicator further comprises an aqueous polymer resin vehicle and an auxiliary agent.

6. A plasma sterilization indicator according to claim 5, wherein the aqueous polymer resin vehicle comprises one or more of a cellulose derivative, an aqueous polybutadiene resin, an aqueous epoxy resin, an aqueous alkyd resin, an aqueous polyester resin, an aqueous polyurethane resin, an aqueous acrylate emulsion.

7. A plasma sterilisation indicator according to claim 6, wherein the cellulose derivative comprises at least one of hydroxymethyl cellulose (CMC), Methyl Cellulose (MC), hydroxyethyl cellulose (HEC), hydroxyethyl methyl cellulose (HEMC), hydroxypropyl cellulose (HPC), hydroxypropyl methyl cellulose (HPMC).

8. A plasma sterilization indicator according to claim 5, wherein the aqueous polymer resin vehicle is formulated from one or two aqueous polyurethane emulsions and one or two aqueous acrylate emulsions.

9. The plasma sterilization indicator of claim 5, wherein the auxiliary agent comprises one or more of a defoamer, a flow aid, a filler, a pigment, a plasticizer, a surfactant, a wetting dispersant, a thickener, a film forming aid, a surfactant; the filler comprises one or more of titanium dioxide, lithopone and zinc oxide.